Buckminsterfullerene, c60, was prepared in gram quantities by contact-arc vaporization of a graphite rod in a 100-Torr atinospherc of helium. followed by extraction of the resultant graphitic soot with toluene. The dominance of C , in this extract was verified by mass, FTIR. and NMR spectroscopy. The molecule was successfully hydrogenated to C6,H,, via a Birch reduction and dehydrogenated back to bare c 6 0 by treatment with DDQ reagent. Cyclic voltammetry of C60 in methylene chloride rcvcaled highly reversible formation of at least two stable anionic forms of c 6 0 in solution. A broad new class of thcsc fulleride and fulleronium ions is anticipated, both with the internal cavity empty and with any one of a large number of elcmcnts inside, thus providing a means of fine-tuning the chemical, optical, and redox properties.
The electronic structure of small Ga x Asy clusters (x + y< 10) are calculated using the local density method. The calculation shows that even-numbered clusters tend to be singlets, as opposed to odd-numbered clusters which are open shell systems. This is in agreement with the experimental observations of even/odd alternations of the electron affinity and ionization potential. In the larger clusters, the atoms prefer an alternating bond arrangement; charge transfers are observed from Ga sites to As sites. This observation is also in agreement with recent chemisorption studies of ammonia on GaAs clusters. The close agreement between theoretical calculations and experimental results, together with the rich variation of electronic properties of GaAs clusters with composition makes GaAs clusters an ideal prototype system for the study of how electronic structure influences chemical reactivity.
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